WO2012119069A2 - Methods for associating or dissociating guest materials with a metal organic framework, systems for associating or dissociating guest materials within a series of metal organic frameworks, thermal energy transfer assemblies, and methods for transferring thermal energy - Google Patents

Methods for associating or dissociating guest materials with a metal organic framework, systems for associating or dissociating guest materials within a series of metal organic frameworks, thermal energy transfer assemblies, and methods for transferring thermal energy Download PDF

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Publication number
WO2012119069A2
WO2012119069A2 PCT/US2012/027458 US2012027458W WO2012119069A2 WO 2012119069 A2 WO2012119069 A2 WO 2012119069A2 US 2012027458 W US2012027458 W US 2012027458W WO 2012119069 A2 WO2012119069 A2 WO 2012119069A2
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Prior art keywords
metal organic
organic framework
metal
framework
guest materials
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PCT/US2012/027458
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French (fr)
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WO2012119069A3 (en
Inventor
B. Peter Mcgrail
Daryl R. BROWN
Praveen K. Thallapally
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Battelle Memorial Institute
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Publication of WO2012119069A2 publication Critical patent/WO2012119069A2/en
Publication of WO2012119069A3 publication Critical patent/WO2012119069A3/en

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
    • B01D53/04—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography with stationary adsorbents
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/50—Carbon dioxide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
    • B01J19/087—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electric or magnetic energy
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B21/00—Nitrogen; Compounds thereof
    • C01B21/04—Purification or separation of nitrogen
    • C01B21/0405—Purification or separation processes
    • C01B21/0411—Chemical processing only
    • C01B21/0427—Chemical processing only by complexation
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B23/00—Noble gases; Compounds thereof
    • C01B23/001—Purification or separation processes of noble gases
    • C01B23/0015—Chemical processing only
    • C01B23/0031—Chemical processing only by complexation
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
    • C01C1/00—Ammonia; Compounds thereof
    • C01C1/003—Storage or handling of ammonia
    • C01C1/006—Storage or handling of ammonia making use of solid ammonia storage materials, e.g. complex ammine salts
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/38—Separation; Purification; Stabilisation; Use of additives
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C7/00—Purification; Separation; Use of additives
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
    • B01D2253/20—Organic adsorbents
    • B01D2253/204—Metal organic frameworks (MOF's)
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/50—Carbon oxides
    • B01D2257/504—Carbon dioxide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2259/00—Type of treatment
    • B01D2259/40—Further details for adsorption processes and devices
    • B01D2259/40083—Regeneration of adsorbents in processes other than pressure or temperature swing adsorption
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25B—REFRIGERATION MACHINES, PLANTS OR SYSTEMS; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS
    • F25B17/00—Sorption machines, plants or systems, operating intermittently, e.g. absorption or adsorption type
    • F25B17/08—Sorption machines, plants or systems, operating intermittently, e.g. absorption or adsorption type the absorbent or adsorbent being a solid, e.g. salt
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
    • Y02C20/00—Capture or disposal of greenhouse gases
    • Y02C20/40—Capture or disposal of greenhouse gases of CO2
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/151—Reduction of greenhouse gas [GHG] emissions, e.g. CO2

Definitions

  • the present disclosure relates to the use of metal organic frameworks.
  • metal organic frameworks have been proposed for use in various capacities. These capacities i nclude but are not limited to the separation of molecules or materials from mixtures that include the molecules or materials. As an example, i n various applications, metal organic frameworks have been proposed for use as materials that can be used to separate carbon dioxide from methane, for example. I n accordance with other applications, metal organic frameworks have also been utilized to retain certain molecules in higher density than they would be retained at when super pressurized . As an example, metal organic frameworks have been proposed for use as hydrogen storage tanks.
  • the metal organic frameworks have been configu red to selectively adsorb or desorb or associate or dissociate certai n materials.
  • the temperature and/or pressure of the metal organic framework can be manipulated , as well as the chemical and/or geometric structure of the metal organic framework, to facilitate either the association or adsorption, or the dissociation or desorption of the specific materials.
  • the present disclosure provides methods for using metal organic frameworks as well as systems that include metal organic frameworks and assemblies that include metal organic frameworks.
  • Methods for releasi ng associated guest materials from a metal organic framework are provided with example methods i ncludi ng alteri ng the oxidation state of at least a portion of the metal of the metal organic framework to dissociate at least a portion of the guest materials from the framework.
  • Example methods for associating guest materials with a metal organic framework are also provided with example methods i ncluding alteri ng the oxidation state of at least a portion of the metal of the metal organic framework to associate at least a portion of the guest materials with the framework.
  • Example methods can i nclude alteri ng the oxidation state of at least a portion of the metal of the metal organic framework to associate or dissociate at least a portion of the guest materials with the framework.
  • Systems for associati ng or dissociating guest materials within a series of metal organic frameworks are provided .
  • Example systems can i nclude at least two individual metal organic frameworks, with one of the individual metal organic frameworks configured to dissociate guest materials, and the other configured to associate guest materials.
  • One framework can include at least some metals of one oxidation state and the other framework can include the same metals of another oxidation state.
  • Example assemblies can i nclude a metal organic framework electrically coupled to a power source ; and a heat transfer assembly associated with the metal organic framework.
  • Example methods can include adsorbing or desorbi ng guest materials to or from a metal organic framework, the adsorbing or desorbing facilitated by changing an oxidation state of at least some of the metal withi n the metal organic framework.
  • the methods can also i nclude providi ng thermal com mu nication between a fluid and one or both of the metal organic framework or the guest materials, with the fluid changing temperatu re upon com mu nication with the one or both of the metal organic framework or the guest materials.
  • Fig . 1 is a configuration of a metal organic framework according to an embodi ment of the disclosure.
  • Fig . 2 represents configu rations of metal organic frameworks according to an embodi ment of the disclosure.
  • Fig.3 represents configurations of metal organic framework and mixtures that include guest materials depicted according to an embodiment of the disclosure.
  • Fig. 4 represents a system including metal organic framework according to an embodiment of the disclosure.
  • Fig. 5 represents a system including metal organic framework according to an embodiment of the disclosure.
  • a metal organic framework configuration 10 that includes metal organic framework 12 conductively coupled via contact 16 and conductive conduit 18 to power source 20.
  • Framework 12 can include metals coupled to organic components.
  • Framework 12 may be configured to define open sites designed to receive guest materials. The open sites may be defined by more than one metal organic complex, for example. At least a portion of the metals of the metal organic framework should be electrically responsive, and more than one metal may be included in metal organic complex 13 having organic portion 14 and metal portion 15.
  • Metal portion 15 of complex 13 can include metals and, according to example implementations, the oxidation state of at least some of the metals will change upon application of differing voltages to the framework.
  • the metals can include transition state metals.
  • Example metals can include Ti, Zr, Hf, Rf, V, Nb, Ta, Db, Cr, Mo, W, Sg, Mn, Tc, Re, Bh, Fe, Ru, Os, Hs, Co, Rh, Os, Hs, Co, Rh, Ir, Mt, Ni, pd, Pt, Ds, Cu, Ag, Au, Zn, and Rg.
  • At least a portion of framework 12 can include one or more of these metals in a charged state.
  • the metal portion can include (Fe 2+ /Fe 3+ ) , and this metal may be complexed as Fe 3 2+ [Fe 3+ (CN) 6 ]2 or Fe 3 3+ [Fe 3+ (CN) 6 ], with the former being a different oxidation state than the latter under differi ng electrical conditions.
  • These mixed valence metal complexes may i nclude tetrakis[4-(pyridyl)oxamethyl]methane as an organic component, for example.
  • the organic portion 1 4 may be referred to as a ligand that coordi nates the metal of the framework.
  • the ligand may be multidentate, for example.
  • the organic portion can be a conductive organic portion.
  • Example organic portions can i nclude but are not limited to straight chain hydrocarbon and/or aromatic ri ngs.
  • the metal organic complex can include metallocenes or calixarenes for example.
  • the ligand of the metal organic complex can be substantially conductive.
  • Example organic portions of the metal organic complex can include but are not li mited to tetrakis[4- (pyridyl)oxamethyl]methane or p-tert-butylcalix[4]arene.
  • Contact 1 6 can be in electrical com munication with at least a portion of the metal of the metal organic framework. I n accordance with example i mplementations, contact 1 6 may be in electrical com mu nication with the organic portion of the metal organic framework and the organic portion can provide electrical com mu nication to at least a portion of the metal of the metal organic framework. Electrical input to contact 1 6 from power source 20 may be controlled with a controller (not shown) . The controller may be programmable and/or may be coupled to a computer operating system (not shown) . I n accordance with example implementations, the controller may be manipulated to provide a desi red voltage to framework 1 2, the voltage corresponding to the association/dissociation of guest materials. Utilizing the power source and the controller voltammetry as well as cyclic voltammetry can be applied to framework 12.
  • Framework 12 of Fig. 1 is depicted without a substrate.
  • framework 12 may be associated with a substrate.
  • framework 12 may be bond to a substrate and/or supported by or within a substrate.
  • framework 12 may be within a housing, such as a conduit, including tubular conduits.
  • framework 12 may be supported by a substrate with the substrate being a substantially open support such as a platform, or in other configurations, framework 12 may be supported by the exterior of a conduit, such as tubular conduit configured to contain framework and/or other materials therein.
  • framework 12 can be applied to or within a substrate as a thin film.
  • framework 12 is depicted having a metal portion 15 (M x ), representing complex 13 having an M x oxidation state. Framework 12 has a voltage Vi being applied thereto to maintain the M x oxidation state.
  • framework 22 is shown having complex 13 with metal portion 25 (M y ), representing the M y oxidation state. Framework 22 has a voltage V 2 being applied thereto to maintain the M y oxidation state.
  • the M x oxidation state is different than the M y oxidation state.
  • the change in oxidation state can be facilitated by altering the voltage applied to the framework.
  • frameworks 12 and 22 can be substantially the same, but with application of ⁇ the oxidation state is M x , and with application of V 2 the oxidation state is M y .
  • the metal of the metal organic framework can be electrochemically altered.
  • the oxidation state of at least some of the metals of the metal organic framework can be changed by altering the voltage applied to the metal and/or the metal organic framework.
  • Vi would be different than V 2 . Referring next to 2(C), at least a portion of the framework 12 is shown having complexes 13 including portion 15 (M x ) having voltage being applied thereto.
  • framework 22 of 2(B) can be altered to reflect framework 12 of 2(C) by altering V 2 to Vi.
  • framework 12 by transitioning from 2(A)-2(C), framework 12 can transition from having metal portions 15 through metal portions 25 to metal portions 15 again.
  • FIG. 3 configurations of metal organic framework and mixtures that include guest materials are depicted according to an embodiment of the disclosure.
  • framework 12 is shown having Vi applied thereto to maintain M x oxidation states of at least some of metal portions 15 of complexes 13.
  • mixture 30 can be exposed or provided to framework 12.
  • Mixture 30 can include guest material 32 ( * ).
  • Material 32 can be a material that is desired to be separated from mixture 30.
  • Example materials include but are not limited to carbon dioxide, and mixture 30 may include components other than carbon dioxide being represented as a remainder of the mixture 34 (#).
  • guest material 32 may be exposed or provided to framework 12 in substantially pure form.
  • carbon dioxide, hydrofluorocarbons (HFC's), refrigerants, N 2 , He, butane, propane, pentane, ammonia, and freon may be desired as a guest material and metal organic frameworks having dynamically modifiable metal portions may be configured to associate with or adsorb same.
  • mixture 30 is provided to framework 12 and at least some of material 32 is retained while material 34 is not.
  • methods for associating guest materials with a metal organic framework are provided with the method including altering the oxidation state of at least a portion of the metal of the metal organic framework to associate at least a portion of the guest materials with the framework.
  • methods for exposing a mixture to the metal organic framework are provided with the mixture comprising the guest materials and other materials, and at least a portion of the other materials not being associated with the metal organic framework upon the exposing.
  • V 2 can be applied to form framework 22 from framework 12 with framework 22 including complexes 13 having metal portions 25 (M y ).
  • a method for releasing associated guest materials from a metal organic framework including altering the oxidation state of at least a portion of the metal of the metal organic framework to dissociate at least a portion of the guest materials from the framework.
  • ⁇ can be applied to again substantially form framework 12 from framework 22 with framework 12 including complexes 13 having metal portions 15 (M x ).
  • mixture 30 can be exposed to framework 12 to associate or adsorb guest material 32 with or to framework 12.
  • assembly 120 can be configured to transfer thermal energy.
  • framework 22 can be configured to dissociate or desorb guest material 32.
  • Guest material 32 can be such a material that when it expands from the associated or adsorbed state it consumes energy in the form of heat from its surroundings.
  • guest material 32 can be provided to a heat transfer assembly such as a mass of coils 124 being configured to be exposed to fluid 124.
  • temperature Ti of guest material 32 can be less than temperature T 2 of guest material 32 after it passes through exchanger 1 22.
  • fluid 1 24 can have a temperature T 3 that is greater than temperature T 4 after being exposed to coils 1 22.
  • framework 22 can include associated or adsorbed guest material such as a refrigerant or carbon dioxide ; can be altered to change the oxidation state of the metal of the metal organic framework thereby dissociating or desorbi ng guest material from the framework.
  • guest material can be allowed to expand via valve 1 26, such as a throttling valve, and be provided to coils 1 22 wherei n the guest material cools fluid 1 24, such as ai r or water, for example.
  • guest material 32 upon passing through exchanger 1 22 may be provided to another metal organic framework configured to associate or adsorb the guest material .
  • thermal energy transfer assemblies of the present disclosure can include a metal organic framework electrically coupled to a power source, and a heat transfer assembly associated with the metal organic framework.
  • the assemblies can further i nclude a controller (not shown) operatively coupled to the metal organic framework and the power sou rce.
  • the assembly can i nclude another metal organic framework coupled to the heat transfer assembly, with the metal of one organic framework having an oxidation state different than the metal of the other organic framework.
  • system 1 30 is shown generally depicting components of an adsorption chiller.
  • guest materials 32 such as a carbon dioxide can be dissociated or desorbed upon providing V 2 to framework 22.
  • this dissociation or desorption fluid 1 24 can be exposed to the thermal energy of framework 22.
  • framework 22 can be supported by a thermally conductive material and configured along the outside of a conduit containi ng fluid 1 24. Fluid 1 24 can be cooled as it passes through this conduit and utilized as desired. Further, guest material 32 can be allowed to condense.
  • guest material 32 can be allowed to at least partially evaporate and associate or adsorb to framework 1 2 at ⁇ .
  • framework 1 2 can increase i n temperatu re and this thermal energy may be provided to fluid 1 30 as it is exposed to framework 1 2.
  • framework 1 2 can be configured along the outside of a conduit contai ning fluid 1 30 to facilitate the heat transfer.
  • the temperatu re of fluid 1 30 upon being exposed to framework 1 2 can be greater than before it was exposed to framework 1 2.
  • assembly 1 30 can be configured as an adsorption chiller. I n accordance with example i mplementations, the adsorption chiller of assembly 1 30 i ncludes an electrochemically d riven desorption and/or adsorption cycle.
  • methods for transferri ng thermal energy including adsorbing or desorbing guest materials to or from a metal organic framework.
  • the adsorbi ng or desorbing can be facilitated by changi ng an oxidation state of at least some of the metal within the metal organic framework.
  • the methods can include providing thermal com munication between a fluid and one or both of the metal organic framework or the guest materials.
  • the fluid can change temperature upon communication with the one or both of the metal organic framework or the guest materials.
  • the providing thermal communication between the metal organic framework and the liquid can i nclude providi ng a conduit havi ng an exterior in thermal contact with the metal organic framework, and providi ng the fluid withi n the conduit.

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Abstract

Methods for releasing associated guest materials from a metal organic framework are provided. Methods for associating guest materials with a metal organic framework are also provided. Methods are provided for selectively associating or dissociating guest materials with a metal organic framework. Systems for associating or dissociating guest materials within a series of metal organic frameworks are provided. Thermal energy transfer assemblies are provided. Methods for transferring thermal energy are also provided.

Description

Methods for Associati ng or Dissociating Guest Materials with a Metal Organic Framework, Systems for Associating or Dissociati ng Guest
Materials Within a Series of Metal Organic Frameworks, Thermal Energy Transfer Assemblies, and Methods for Transferri ng Thermal
Energy
CROSS REFERENCE TO RELATED APPLICATION
This application claims priority to U nited States Provisional Patent Application No. 61 /448,965 which was filed on March 3, 201 1 , entitled "Methods for Associating or Dissociati ng Guest Materials with a Metal Organic Framework, Systems for Associati ng or Dissociating Guest Materials Withi n a Series of Metal Organic Frameworks, Thermal Energy Transfer Assemblies, and Methods for Transferring Thermal Energy", the enti rety of which is incorporated by reference herein .
STATEMENT AS TO RIGHTS TO INVENTIONS MADE UNDER FEDERALLY-SPONSORED RESEARCH AND DEVELOPMENT
This invention was made with Government support u nder Contract D E-AC0576 RLO1 830 awarded by the U .S. Department of Energy. The Govern ment has certai n rig hts i n the i nvention .
TECHNICAL FIELD
The present disclosure relates to the use of metal organic frameworks.
BACKGROUND Recently, metal organic frameworks have been proposed for use in various capacities. These capacities i nclude but are not limited to the separation of molecules or materials from mixtures that include the molecules or materials. As an example, i n various applications, metal organic frameworks have been proposed for use as materials that can be used to separate carbon dioxide from methane, for example. I n accordance with other applications, metal organic frameworks have also been utilized to retain certain molecules in higher density than they would be retained at when super pressurized . As an example, metal organic frameworks have been proposed for use as hydrogen storage tanks.
I n these applications, in the past, the metal organic frameworks have been configu red to selectively adsorb or desorb or associate or dissociate certai n materials. As an example, the temperature and/or pressure of the metal organic framework can be manipulated , as well as the chemical and/or geometric structure of the metal organic framework, to facilitate either the association or adsorption, or the dissociation or desorption of the specific materials.
The present disclosure provides methods for using metal organic frameworks as well as systems that include metal organic frameworks and assemblies that include metal organic frameworks.
SUMMARY
Methods for releasi ng associated guest materials from a metal organic framework are provided with example methods i ncludi ng alteri ng the oxidation state of at least a portion of the metal of the metal organic framework to dissociate at least a portion of the guest materials from the framework. Example methods for associating guest materials with a metal organic framework are also provided with example methods i ncluding alteri ng the oxidation state of at least a portion of the metal of the metal organic framework to associate at least a portion of the guest materials with the framework.
Methods are provided for selectively associating or dissociati ng guest materials with a metal organic framework. Example methods can i nclude alteri ng the oxidation state of at least a portion of the metal of the metal organic framework to associate or dissociate at least a portion of the guest materials with the framework. Systems for associati ng or dissociating guest materials within a series of metal organic frameworks are provided . Example systems can i nclude at least two individual metal organic frameworks, with one of the individual metal organic frameworks configured to dissociate guest materials, and the other configured to associate guest materials. One framework can include at least some metals of one oxidation state and the other framework can include the same metals of another oxidation state.
Thermal energy transfer assemblies are provided. Example assemblies can i nclude a metal organic framework electrically coupled to a power source ; and a heat transfer assembly associated with the metal organic framework.
Methods for transferri ng thermal energy are also provided . Example methods can include adsorbing or desorbi ng guest materials to or from a metal organic framework, the adsorbing or desorbing facilitated by changing an oxidation state of at least some of the metal withi n the metal organic framework. The methods can also i nclude providi ng thermal com mu nication between a fluid and one or both of the metal organic framework or the guest materials, with the fluid changing temperatu re upon com mu nication with the one or both of the metal organic framework or the guest materials.
BRIEF DESCRIPTION OF THE DRAWINGS
Embodi ments of the disclosure are described below with reference to the following accompanyi ng drawings. Fig . 1 is a configuration of a metal organic framework according to an embodi ment of the disclosure.
Fig . 2 represents configu rations of metal organic frameworks according to an embodi ment of the disclosure. Fig.3 represents configurations of metal organic framework and mixtures that include guest materials depicted according to an embodiment of the disclosure.
Fig. 4 represents a system including metal organic framework according to an embodiment of the disclosure.
Fig. 5 represents a system including metal organic framework according to an embodiment of the disclosure.
DESCRIPTION
The methods, systems, and assemblies of the present disclosure will be described with reference to Figs. 1-5. Referring first to Fig. 1, a metal organic framework configuration 10 is shown that includes metal organic framework 12 conductively coupled via contact 16 and conductive conduit 18 to power source 20. Framework 12 can include metals coupled to organic components. Framework 12 may be configured to define open sites designed to receive guest materials. The open sites may be defined by more than one metal organic complex, for example. At least a portion of the metals of the metal organic framework should be electrically responsive, and more than one metal may be included in metal organic complex 13 having organic portion 14 and metal portion 15.
Metal portion 15 of complex 13 can include metals and, according to example implementations, the oxidation state of at least some of the metals will change upon application of differing voltages to the framework. The metals can include transition state metals. Example metals can include Ti, Zr, Hf, Rf, V, Nb, Ta, Db, Cr, Mo, W, Sg, Mn, Tc, Re, Bh, Fe, Ru, Os, Hs, Co, Rh, Os, Hs, Co, Rh, Ir, Mt, Ni, pd, Pt, Ds, Cu, Ag, Au, Zn, and Rg. At least a portion of framework 12 can include one or more of these metals in a charged state.
For example metal portion 15 can include mixed valence metals (M2+/M3+) complexed with the organic portion; M2+=Fe, Cd, Co, Cu, M n, Ni , and Zn ; and M = Fe or Co, for example. Accordi ng to specific i mplementations, the metal portion can include (Fe2+/Fe3+) , and this metal may be complexed as Fe3 2+[Fe3+(CN) 6]2 or Fe3 3+[Fe3+(CN)6], with the former being a different oxidation state than the latter under differi ng electrical conditions. These mixed valence metal complexes may i nclude tetrakis[4-(pyridyl)oxamethyl]methane as an organic component, for example.
I n accordance with example implementations, the organic portion 1 4 may be referred to as a ligand that coordi nates the metal of the framework. The ligand may be multidentate, for example. The organic portion can be a conductive organic portion. Example organic portions can i nclude but are not limited to straight chain hydrocarbon and/or aromatic ri ngs. The metal organic complex can include metallocenes or calixarenes for example. I n accordance with example i mplementations, the ligand of the metal organic complex can be substantially conductive. Example organic portions of the metal organic complex can include but are not li mited to tetrakis[4- (pyridyl)oxamethyl]methane or p-tert-butylcalix[4]arene.
Contact 1 6 can be in electrical com munication with at least a portion of the metal of the metal organic framework. I n accordance with example i mplementations, contact 1 6 may be in electrical com mu nication with the organic portion of the metal organic framework and the organic portion can provide electrical com mu nication to at least a portion of the metal of the metal organic framework. Electrical input to contact 1 6 from power source 20 may be controlled with a controller (not shown) . The controller may be programmable and/or may be coupled to a computer operating system (not shown) . I n accordance with example implementations, the controller may be manipulated to provide a desi red voltage to framework 1 2, the voltage corresponding to the association/dissociation of guest materials. Utilizing the power source and the controller voltammetry as well as cyclic voltammetry can be applied to framework 12.
Framework 12 of Fig. 1 is depicted without a substrate. In accordance with example implementations, framework 12 may be associated with a substrate. In specific implementations, framework 12 may be bond to a substrate and/or supported by or within a substrate. In accordance with example configurations, framework 12 may be within a housing, such as a conduit, including tubular conduits. In accordance with other configurations, framework 12 may be supported by a substrate with the substrate being a substantially open support such as a platform, or in other configurations, framework 12 may be supported by the exterior of a conduit, such as tubular conduit configured to contain framework and/or other materials therein. In accordance with example implementations, framework 12 can be applied to or within a substrate as a thin film.
Referring next to Fig. 2, configurations of metal organic frameworks according to an embodiment of the disclosure are shown. Referring first to 2(A), framework 12 is depicted having a metal portion 15 (Mx), representing complex 13 having an Mx oxidation state. Framework 12 has a voltage Vi being applied thereto to maintain the Mx oxidation state. Referring next to 2(B), framework 22 is shown having complex 13 with metal portion 25 (My), representing the My oxidation state. Framework 22 has a voltage V2 being applied thereto to maintain the My oxidation state. In accordance with example implementations, the Mx oxidation state is different than the My oxidation state. The change in oxidation state can be facilitated by altering the voltage applied to the framework. As an example, frameworks 12 and 22 can be substantially the same, but with application of \ the oxidation state is Mx, and with application of V2 the oxidation state is My. In accordance with example implementations, the metal of the metal organic framework can be electrochemically altered. According to example implementations the oxidation state of at least some of the metals of the metal organic framework can be changed by altering the voltage applied to the metal and/or the metal organic framework. In example implementations Vi would be different than V2. Referring next to 2(C), at least a portion of the framework 12 is shown having complexes 13 including portion 15 (Mx) having voltage being applied thereto. In accordance with example implementations, framework 22 of 2(B) can be altered to reflect framework 12 of 2(C) by altering V2 to Vi. According to specific implementations, by transitioning from 2(A)-2(C), framework 12 can transition from having metal portions 15 through metal portions 25 to metal portions 15 again.
Referring next to Fig. 3, configurations of metal organic framework and mixtures that include guest materials are depicted according to an embodiment of the disclosure. Referring first to 3(A), framework 12 is shown having Vi applied thereto to maintain Mx oxidation states of at least some of metal portions 15 of complexes 13.
In accordance with example implementations, mixture 30 can be exposed or provided to framework 12. Mixture 30 can include guest material 32 (*). Material 32 can be a material that is desired to be separated from mixture 30. Example materials include but are not limited to carbon dioxide, and mixture 30 may include components other than carbon dioxide being represented as a remainder of the mixture 34 (#). In accordance with other implementations, guest material 32 may be exposed or provided to framework 12 in substantially pure form. For example, carbon dioxide, hydrofluorocarbons (HFC's), refrigerants, N2, He, butane, propane, pentane, ammonia, and freon may be desired as a guest material and metal organic frameworks having dynamically modifiable metal portions may be configured to associate with or adsorb same.
In accordance with 3(A), mixture 30 is provided to framework 12 and at least some of material 32 is retained while material 34 is not. Accordingly, methods for associating guest materials with a metal organic framework are provided with the method including altering the oxidation state of at least a portion of the metal of the metal organic framework to associate at least a portion of the guest materials with the framework. Further, methods for exposing a mixture to the metal organic framework are provided with the mixture comprising the guest materials and other materials, and at least a portion of the other materials not being associated with the metal organic framework upon the exposing. Referring to 3(B), V2 can be applied to form framework 22 from framework 12 with framework 22 including complexes 13 having metal portions 25 (My). Upon changing at least some of the oxidation state of Mx to My, at least some of guest material 32 dissociates or desorbs from framework 22 as substantially pure guest material 32. Accordingly, a method for releasing associated guest materials from a metal organic framework is provided with the method including altering the oxidation state of at least a portion of the metal of the metal organic framework to dissociate at least a portion of the guest materials from the framework. Referring to 3(C), \ can be applied to again substantially form framework 12 from framework 22 with framework 12 including complexes 13 having metal portions 15 (Mx). Upon returning the oxidation state of My to Mx, mixture 30 can be exposed to framework 12 to associate or adsorb guest material 32 with or to framework 12.
Referring to Fig. 4, assembly 120 is shown that can be configured to transfer thermal energy. In accordance with example implementations, framework 22 can be configured to dissociate or desorb guest material 32. Guest material 32 can be such a material that when it expands from the associated or adsorbed state it consumes energy in the form of heat from its surroundings. Accordingly, guest material 32 can be provided to a heat transfer assembly such as a mass of coils 124 being configured to be exposed to fluid 124. Accordingly, temperature Ti of guest material 32 can be less than temperature T2 of guest material 32 after it passes through exchanger 1 22. Fu rther, fluid 1 24 can have a temperature T3 that is greater than temperature T4 after being exposed to coils 1 22. I n accordance with example implementations, framework 22 can include associated or adsorbed guest material such as a refrigerant or carbon dioxide ; can be altered to change the oxidation state of the metal of the metal organic framework thereby dissociating or desorbi ng guest material from the framework. Upon dissociation the guest material can be allowed to expand via valve 1 26, such as a throttling valve, and be provided to coils 1 22 wherei n the guest material cools fluid 1 24, such as ai r or water, for example. I n accordance with example implementations, guest material 32 upon passing through exchanger 1 22 may be provided to another metal organic framework configured to associate or adsorb the guest material .
Accordingly, thermal energy transfer assemblies of the present disclosure can include a metal organic framework electrically coupled to a power source, and a heat transfer assembly associated with the metal organic framework. I n accordance with specific i mplementations, the assemblies can further i nclude a controller (not shown) operatively coupled to the metal organic framework and the power sou rce. Additionally, the assembly can i nclude another metal organic framework coupled to the heat transfer assembly, with the metal of one organic framework having an oxidation state different than the metal of the other organic framework.
Referri ng to Fig. 5, system 1 30 is shown generally depicting components of an adsorption chiller. Referring fi rst to (A) , guest materials 32 such as a carbon dioxide can be dissociated or desorbed upon providing V2 to framework 22. During this dissociation or desorption fluid 1 24 can be exposed to the thermal energy of framework 22. I n accordance with example implementations, framework 22 can be supported by a thermally conductive material and configured along the outside of a conduit containi ng fluid 1 24. Fluid 1 24 can be cooled as it passes through this conduit and utilized as desired. Further, guest material 32 can be allowed to condense.
Referri ng next to (B) , guest material 32 can be allowed to at least partially evaporate and associate or adsorb to framework 1 2 at \ . During adsorption , framework 1 2 can increase i n temperatu re and this thermal energy may be provided to fluid 1 30 as it is exposed to framework 1 2. I n accordance with example implementations, framework 1 2 can be configured along the outside of a conduit contai ning fluid 1 30 to facilitate the heat transfer. Accordi ngly, the temperatu re of fluid 1 30 upon being exposed to framework 1 2 can be greater than before it was exposed to framework 1 2. Accordi ngly, assembly 1 30 can be configured as an adsorption chiller. I n accordance with example i mplementations, the adsorption chiller of assembly 1 30 i ncludes an electrochemically d riven desorption and/or adsorption cycle.
Accordingly, methods for transferri ng thermal energy are provided with the methods including adsorbing or desorbing guest materials to or from a metal organic framework. The adsorbi ng or desorbing can be facilitated by changi ng an oxidation state of at least some of the metal within the metal organic framework. The methods can include providing thermal com munication between a fluid and one or both of the metal organic framework or the guest materials. The fluid can change temperature upon communication with the one or both of the metal organic framework or the guest materials. Accordi ng to example i mplementations, the providing thermal communication between the metal organic framework and the liquid can i nclude providi ng a conduit havi ng an exterior in thermal contact with the metal organic framework, and providi ng the fluid withi n the conduit.

Claims

CLAI MS The invention clai med is :
1 . A method for releasing associated guest materials from a metal organic framework, the method comprising altering the oxidation state of at least a portion of the metal of the metal organic framework to dissociate at least a portion of the guest materials from the
framework.
2. The method of clai m 1 wherein the portion of the metal of the metal organic framework is a transition metal.
3. The method of clai m 1 wherein the portion of the metal of the metal organic framework is one or more of Ti , Zr, Hf, Rf, V, Nb, Ta, Db, Cr, Mo, W, Sg, Mn , Tc, Re, Bh, Fe, Ru , Os, Hs, Co, Rh, Os, Hs, Co, Rh, I r, Mt, Ni, pd, Pt, Ds, Cu, Ag, Au, and Rg .
4. The method of clai m 1 wherein the portion of the metal of the metal organic framework has a mixed oxidation state.
5. The method of clai m 1 wherein the portion of the metal of the metal organic framework is represented as (M2+/M3+) .
6. The method of clai m 1 wherein the portion of the metal of the metal organic framework is coupled to a substantially conductive organic ligand .
7. The method of clai m 1 wherein the guest material comprises carbon dioxide.
8. A method for associati ng guest materials with a metal organic framework, the method comprisi ng alteri ng the oxidation state of at least a portion of the metal of the metal organic framework to associate at least a portion of the guest materials with the framework.
9. The method of claim 8 further comprising exposing a mixture to the metal organic framework, the mixture comprising the guest materials and other materials, at least a portion of the other materials not being associated with the metal organic framework upon the exposing.
10. A method for selectively associating or dissociating guest materials with a metal organic framework, the method comprising altering the oxidation state of at least a portion of the metal of the metal organic framework to associate or dissociate at least a portion of the guest materials with the framework.
11. The method of claim 10 further comprising exposing a mixture to the metal organic framework, the mixture comprising the guest materials and other materials, at least a portion of the other materials not being associated with the metal organic framework upon the exposing.
12. The method of claim 11 wherein during the exposing, guest material is associated with the metal organic framework.
13. The method of claim 12 further comprising:
ceasing the exposing;
altering the oxidation state of the portion of the metal; and dissociating at least a portion of the guest materials from the metal organic framework.
14. The method of claim 13 further comprising:
after the dissociating, altering the oxidation state of the portion of the metal to return the oxidation state to an associating oxidation state;
after the altering, exposing the mixture to the metal organic framework; and
associating at least a portion of the guest material of the mixture with the metal organic framework.
15. The method of claim 10 wherein the altering comprises applying a predetermined voltage to the metal organic framework.
16. The method of claim 10 wherein the oxidation state of the portion of the metal is electrochemically altered.
17. A system for associating or dissociating guest materials within a series of metal organic frameworks, the system comprising at least two individual metal organic frameworks, one of the individual metal organic frameworks configured to dissociate and the other configured to associate guest materials, wherein the one framework comprises at least some metals of one oxidation state and the other framework comprises the same metals of another oxidation state.
18. The system of claim 17 further comprising:
a power source; and
a controller operatively coupled to both the power source and the metal organic frameworks.
19. The system of claim 17 wherein the metal of the metal organic frameworks are mixed valence transition metals.
20. The system of claim 18 wherein the one metal organic
framework comprises (M2+/M3+), and the other metal organic
framework comprises (M3+/M3+).
21. The system of claim 17 further comprising a conduit extending to a valve in fluid communication with both the metal organic
frameworks.
22. The system of claim 21 further comprising:
a power source;
a motor configured to operate the valve; and
a controller operatively coupled to the power source, the metal organic frameworks, and the motor.
23. A thermal energy transfer assembly, the assembly comprising : a metal organic framework electrically coupled to a power source ; and
a heat transfer assembly associated with the metal organic framework.
24. The assembly of clai m 23 further comprising a conduit
extending between the metal organic framework and the heat transfer assembly.
25. The assembly of clai m 24 further comprising a th rottling valve between the metal organic framework and the heat transfer assembly.
26. The assembly of clai m 25 further comprising a controller operatively coupled to the metal organic framework and the power source.
27. The assembly of clai m 23 further comprising another metal organic framework coupled to the heat transfer assembly, the metal of the one organic framework having an oxidation state different than the metal of the other organic framework.
28. The assembly of clai m 23 further comprising another metal organic framework associated with another heat transfer assembly, the metal of the one organic framework having an oxidation state different than the metal of the other organic framework.
29. The assembly of clai m 28 wherei n the assembly is configured as an adsorption chiller.
30. A method for transferri ng thermal energy, the method
comprisi ng :
adsorbing or desorbing guest materials to or from a metal organic framework, the adsorbi ng or desorbi ng facilitated by changi ng an oxidation state of at least some of the metal within the metal organic framework; and
providi ng thermal com mu nication between a fluid and one or both of the metal organic framework or the guest materials, the fluid changing temperatu re upon com munication with the one or both of the metal organic framework or the guest materials.
31 . The method of clai m 30 wherein the adsorbing guest materials increases the temperatu re of the metal organic framework.
32. The method of clai m 30 wherein the desorbing the guest materials decreases the temperature of the metal organic framework.
33. The method of clai m 30 wherein the providing thermal
com mu nication between the metal organic framework and the liquid comprises providing a conduit having an exterior i n thermal contact with the metal organic framework, and providi ng the fluid withi n the conduit.
PCT/US2012/027458 2011-03-03 2012-03-02 Methods for associating or dissociating guest materials with a metal organic framework, systems for associating or dissociating guest materials within a series of metal organic frameworks, thermal energy transfer assemblies, and methods for transferring thermal energy WO2012119069A2 (en)

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